CN113646406B - Phosphor powder, composite, and light-emitting device - Google Patents

Phosphor powder, composite, and light-emitting device Download PDF

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CN113646406B
CN113646406B CN202080025108.XA CN202080025108A CN113646406B CN 113646406 B CN113646406 B CN 113646406B CN 202080025108 A CN202080025108 A CN 202080025108A CN 113646406 B CN113646406 B CN 113646406B
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phosphor
phosphor powder
light
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particles
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野见山智宏
武田雄介
山浦太阳
奥园达也
宫崎胜
渡边真太郎
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Denka Co Ltd
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    • H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
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Abstract

One embodiment of the present invention is a phosphor powder comprising Eu-containing α -type sialon phosphor particles. The phosphor powder has P1 as an internal quantum efficiency after being held at 600 ℃ for 1 hour in an atmospheric atmosphere and P2 as an internal quantum efficiency after being held at 700 ℃ for 1 hour in an atmospheric atmosphere, wherein P1 is 70% or more and (P1-P2)/P1X 100 is 2.8% or less.

Description

Phosphor powder, composite, and light-emitting device
Technical Field
The present invention relates to a phosphor powder, a composite, and a light-emitting device.
Background
As a nitride or oxynitride phosphor, an α -sialon phosphor obtained by activating a specific rare earth element is known to have useful fluorescence characteristics, and is applied to a white LED and the like. In the α -sialon phosphor, the Si — N bond of the α -type silicon nitride crystal is partially replaced by an Al — N bond and an Al — O bond, and a specific element (Ca, li, mg, and Y, or a lanthanoid metal excluding La and Ce) is incorporated and dissolved in the crystal lattice to maintain electrical neutrality. The fluorescent property is exhibited by using a rare earth element as a part of the element which enters the solid solution and becomes a luminescence center. Among them, an α -sialon phosphor obtained by dissolving Ca in a solid solution and substituting a part thereof with Eu is excited relatively efficiently in a wide wavelength region from the ultraviolet region to the cyan region, and exhibits yellow to orange emission. As an attempt to further improve the fluorescence characteristics of such an α -sialon phosphor, for example, it has been proposed to select an α -sialon phosphor having a specific average particle size by classification (patent document 1).
Documents of the prior art
Patent document
Patent document 1: japanese laid-open patent publication No. 2009-96882
Disclosure of Invention
In recent years, further enhancement of luminance of white LEDs is strongly desired. For example, further improvement in light emission characteristics of phosphor powder for white LEDs is required.
The present invention has been made in view of the above problems. The present invention aims to provide a phosphor powder having improved emission characteristics.
According to the present invention, there is provided a phosphor powder comprising Eu-containing α -type sialon phosphor particles, wherein P1 is 70% or more and (P1-P2)/P1 × 100 is 2.8% or less, where P1 is the internal quantum efficiency after 1 hour at 600 ℃ in an atmospheric atmosphere and P2 is the internal quantum efficiency after 1 hour at 700 ℃ in an atmospheric atmosphere.
Further, the present invention provides a composite comprising the phosphor powder and a sealing material for sealing the phosphor powder.
Further, according to the present invention, there is provided a light-emitting device including a light-emitting element that emits excitation light and the complex that converts the wavelength of the excitation light.
Effects of the invention
According to the present invention, a technique relating to a phosphor powder having improved emission characteristics can be provided.
Drawings
Fig. 1 is a schematic sectional view showing a structure of a light-emitting device according to an embodiment.
Detailed Description
Hereinafter, embodiments of the present invention will be described in detail.
The phosphor powder according to the embodiment is a phosphor powder composed of α -type sialon phosphor particles containing Eu. When the phosphor powder is held at 600 ℃ for 1 hour in the air atmosphere and the internal quantum efficiency is P1 and P2 after held at 700 ℃ for 1 hour in the air atmosphere, P1 is 70% or more and (P1-P2)/P1X 100 is 2.8% or less.
According to the phosphor powder of the present embodiment, the fluorescence characteristics of the conventional α -sialon phosphor particles can be improved while maintaining the excitation wavelength region and the fluorescence wavelength region. Therefore, as a result, the light-emitting characteristics of the light-emitting device using the phosphor powder of the present embodiment can be improved.
For this reason, although the detailed mechanism is not yet established, it is presumed that the phosphor powder satisfying the requirement that P1 is 70% or more and (P1-P2)/P1 × 100 is 2.8% or less has high surface chemical stability, and elements and compounds which do not contribute to fluorescence are sufficiently removed. Therefore, it is considered that the high fluorescence characteristics can be stably obtained even in a state where the heating is not performed.
(alpha-sialon phosphor particle)
The α -type sialon phosphor particles containing Eu are composed of an α -type sialon phosphor described below.
The alpha-sialon phosphor is of the general formula: (M1) x ，M2 y ，Eu z )(Si 12－(m+n) Al m+n )(O n N 16－n ) (wherein M1 is a 1-valent Li element, and M2 is 1 or more 2-valent elements selected from Mg, ca and lanthanides (excluding La and Ce)).
The solid solution composition of the alpha-sialon phosphor is represented by x, y, z of the above general formula and m and N determined by the Si/Al ratio and O/N ratio accompanying them, and is 0. Ltoreq. X < 2.0, 0. Ltoreq. Y < 2.0, 0. Ltoreq. Z < 0.5, 0. Ltoreq. X + y, 0.3. Ltoreq. X + y + z < 2.0, 0. Ltoreq. M < 4.0, 0. Ltoreq. N < 3.0. In particular, when Ca is used as M2, the α -sialon phosphor is stabilized in a wide composition range, and a part of it is substituted with Eu, which is an emission center, and excited by light in a wide wavelength range from ultraviolet to cyan, thereby obtaining a phosphor exhibiting visible light emission of yellow to orange.
In addition, from the viewpoint of obtaining light of a bulb color in illumination applications, the α -sialon phosphor preferably does not contain Li as a solid solution composition or contains a small amount of Li. In the above general formula, it is preferable that 0. Ltoreq. X.ltoreq.0.1. And/or the ratio of Li in the α -sialon phosphor is preferably 0 to 1 mass%.
In general, since an α -type sialon phosphor has a second crystal phase different from that of the α -type sialon phosphor and an amorphous phase inevitably present, a solid solution composition cannot be strictly defined by composition analysis or the like. The α -sialon phosphor is preferably an α -sialon single phase as a crystal phase, and aluminum nitride, a polytype thereof, or the like may be contained as another crystal phase.
In the α -sialon phosphor particles, a plurality of equiaxed primary particles are sintered to form massive secondary particles. The primary particles in the present embodiment are the smallest particles that can exist alone and can be observed with an electron microscope or the like. The shape of the α -sialon phosphor particle is not particularly limited. Examples of the shape include a spherical body, a cubic body, a columnar body, and an irregular shape.
Average particle diameter or median diameter (D) of particles of alpha-sialon phosphor 50 ) The lower limit of (B) is preferably 1 μm or more, more preferably 5 μm or more, and further preferably 10 μm or more. Further, the average particle diameter or the median diameter (D) of the particles of the alpha-sialon phosphor 50 ) The upper limit of (B) is preferably 30 μm or less, more preferably 20 μm or less. Average particle diameter or median particle diameter (D) of alpha-sialon phosphor particles 50 ) Is the size of the secondary particles. By fluorescing alpha-sialonThe average or median diameter (D) of the bulk particles 50 ) The transparency of the composite described later can be further improved by setting the thickness to 5 μm or more. On the other hand, the average particle diameter or the median diameter (D) of the particles of the alpha-sialon phosphor is determined 50 ) The particle size is 30 μm or less, so that generation of chips can be suppressed when the composite is cut and processed by a cutter or the like.
Here, the average particle size of the α -sialon phosphor particles is defined by the following formula in JIS R1629:1997, 50% of the volume-based cumulative fraction obtained by the laser diffraction scattering method.
Here, the median diameter (D) of the phosphor powder 50 ) Means based on JIS R1629:1997 median particle diameter (D) in volume-based cumulative fraction by laser diffraction scattering 50 )。
The phosphor powder of the present embodiment has P1 as an internal quantum efficiency after being held at 600 ℃ for 1 hour in an atmospheric atmosphere, P2 as an internal quantum efficiency after being held at 700 ℃ for 1 hour in an atmospheric atmosphere, and P3 as an internal quantum efficiency after being held at 800 ℃ for 1 hour in an atmospheric atmosphere, wherein P1 is 70% or more and (P1-P2)/P1 × 100 is 2.8% or less.
Here, the internal quantum efficiency of the phosphor powder can be measured by a spectrophotometer equipped with an integrating sphere.
The internal quantum efficiency after 1 hour of holding at each of the above temperatures can be regarded as an index of the chemical stability of the surface of the α -sialon phosphor particle. It is considered that the indices defined by P1 and (P1-P2)/P1 × 100 of the phosphor powder of the present embodiment satisfy the above conditions, and the chemical stability of the surface is extremely higher than that of the conventional phosphor powder.
(P1-P2)/P1X 100 is more preferably 1.5% or less. This makes it possible to form phosphor powder having a surface with higher chemical stability.
In the phosphor powder of the present embodiment, it is preferable that P2 is 68% or more, except that the index defined by P1 and (P1-P2)/P1 × 100 satisfies the above condition. Accordingly, the chemical stability of the surface of the α -sialon phosphor particle can be further improved.
In addition to the above conditions, the phosphor powder of the present embodiment preferably has a P3 of 68% or more. Accordingly, the chemical stability of the surface of the α -sialon phosphor particle can be further improved.
The phosphor powder described above can improve the fluorescence characteristics by satisfying the conditions that P1 is 70% or more and (P1-P2)/P1 × 100 is 2.8% or less.
(other characteristics)
The phosphor powder of the present embodiment preferably satisfies other characteristics in addition to the characteristics relating to P1, (P1-P2)/P1 × 100 described above.
As an example of the characteristics, the following [ extracted ion analysis A ] was used for phosphor powder]The concentration C of the ammonium ion of the phosphor powder obtained A Preferably 15ppm to 100ppm, more preferably 15ppm to 80ppm, and still more preferably 15ppm to 60ppm.
Consider C A In particular, if the chemical stability of the surface of the phosphor particles is improved, the mother crystal of the phosphor contributing to fluorescence is easily and stably present, and thus the fluorescence characteristics can be further improved.
[ extracted ion analysis A ]
0.5g of phosphor powder was put into 25mL of distilled water in a PTFE (polytetrafluoroethylene) container with a lid, and the mixture was held at 60 ℃ for 24 hours. Thereafter, the total mass M of ammonia ions contained in the aqueous solution from which the solid content was removed by filtration was determined by ion chromatography A . Then, with M A Dividing by the mass of the phosphor powder to obtain C A . I.e. C A Is an index indicating the amount of ammonia ions per unit mass of the phosphor powder (solid state).
If the description is complemented, M A The ammonia ion concentration of the aqueous solution measured by ion chromatography can be multiplied by the mass (25 g) of water used.
In addition, C A By using M A Divided by the mass (0.5 g) of the phosphor powder to be analyzed.
At M A Is not only a sheetIn the case of a bit of "g (g)", C A [ unit: ppm of]Can be obtained by applying M A [ unit: g]The value obtained by dividing the mass of the phosphor powder (0.5 g) by the weight of the phosphor powder was multiplied by 10 6 And then the result is obtained.
As another example of the characteristics, the diffuse reflectance of the phosphor powder to light having a wavelength of 600nm is preferably 93% to 99%, more preferably 94% to 96%. The diffuse reflectance can be measured by an ultraviolet-visible spectrophotometer equipped with an integrating sphere device. The measurement method can be also referred to in the examples described later.
Diffuse reflectance is an index indicating the degree of diffuse reflection of light. That is, the diffuse reflectance may be related to the surface state of the phosphor particles, the particle size distribution of the phosphor powder, and the like. The details are not clear, and it is estimated that the diffuse reflectance of the phosphor powder with respect to light having a wavelength of 600nm in the above numerical range indicates that, for example, a heterogeneous phase that does not contribute to fluorescence is sufficiently removed from the surface of the phosphor particles.
In the present embodiment, the median particle diameter D of the phosphor powder is preferred from the viewpoint of particularly good fluorescence characteristics (such as luminous efficiency) 50 10 to 20 μm and a diffuse reflectance for light having a wavelength of 600nm within the above numerical range.
(method for producing phosphor powder)
A method for producing a phosphor powder composed of α -sialon phosphor particles according to this embodiment will be described. In the α -sialon phosphor particles, a part of the raw material powder mainly reacts during the synthesis process to form a liquid phase, and each element moves through the liquid phase, thereby forming a solid solution and growing particles.
First, raw materials containing elements constituting the Eu-containing α -type sialon phosphor particles are mixed. In alpha-sialon phosphor particles synthesized using calcium nitride as a calcium raw material and having a low oxygen content, calcium is dissolved in a high concentration. In particular, when the Ca solid solution concentration is high, a phosphor having an emission peak wavelength on a higher wavelength side (590 nm or more, more specifically, 590nm to 610nm, and even more specifically, 592nm to 608 nm) than the conventional composition using an oxide raw material can be obtained. Specifically, in the above general formula, 1.5 < x + y + z.ltoreq.2.0 is preferable. Fine adjustment of the emission spectrum may also be performed by substituting a part of Ca for Li, mg, sr, ba, Y, and lanthanoid (excluding La and Ce).
As the raw material powder other than the above, silicon nitride, aluminum nitride, and Eu compound are exemplified. As the Eu compound, europium oxide, a compound which becomes europium oxide after heating, and europium nitride are available. Europium nitride which can reduce the amount of oxygen in the system is preferable.
When a proper amount of α -sialon phosphor particles synthesized in advance is added to the raw material powder, α -sialon phosphor particles having a relatively large minor axis diameter can be obtained as a starting point of particle growth, and the particle shape can be controlled by changing the form of the α -sialon particles added.
As a method of mixing the above-mentioned raw materials, there are a dry mixing method, and a method of wet mixing in an inert solvent which does not substantially react with each component of the raw materials, and then removing the solvent. Examples of the mixing device include a V-type mixer, a swing type mixer, a ball mill, and a vibration mill. Mixing of calcium nitride, which is unstable in the atmosphere, is performed in a glove box in an inert atmosphere because hydrolysis and oxidation thereof affect the characteristics of the synthetic product.
The mixed powder (hereinafter, simply referred to as "raw material powder") is filled in a container made of a material having low reactivity with the raw material and the synthesized phosphor, for example, a container made of boron nitride. Subsequently, the mixture was heated in a nitrogen atmosphere for a predetermined time. Thus, an α -sialon phosphor was obtained. The temperature of the heat treatment is preferably 1650 ℃ to 1950 ℃.
By setting the temperature of the heat treatment to 1650 ℃ or higher, the amount of unreacted product remaining can be suppressed, and primary particles can be sufficiently grown. Further, by setting the temperature to 1950 ℃ or lower, significant sintering between particles can be suppressed.
From the viewpoint of suppressing sintering between particles during heating, it is preferable to increase the volume of the raw material powder filled in the container. Specifically, it is preferable that the bulk density of the raw material powder is set to 0.6g/cm when the container is filled with the raw material powder 3 The following.
The heating time in the heat treatment is preferably 2 to 24 hours, as a time range in which a large amount of unreacted materials, insufficient primary particle growth, or sintering between particles does not occur.
The above-described steps produce an α -sialon phosphor having an ingot-like outer shape. The secondary particles of the secondary particles-adjusted D can be obtained by subjecting the ingot-shaped α -sialon phosphor to a pulverization step using a pulverizer such as a crusher, mortar mill, ball mill, vibration mill or jet mill, and a sieve classification step after the pulverization step 50 A phosphor powder comprising α -sialon phosphor particles having a particle diameter. Further, the step of dispersing the dispersion in an aqueous solution to remove secondary particles having a small particle diameter and being less likely to settle can be performed to adjust D of the secondary particles 50 And (4) the particle size.
The phosphor powder composed of α -sialon phosphor particles according to the embodiment can be produced by performing the above-described steps and then performing an acid treatment step.
In the acid treatment step, for example, α -sialon phosphor particles are immersed in an acidic aqueous solution. Examples of the acidic aqueous solution include an acidic aqueous solution containing 1 acid selected from hydrofluoric acid, nitric acid, hydrochloric acid, and the like, and a mixed acid aqueous solution obtained by mixing 2 or more of the above acids. Among them, a hydrofluoric acid aqueous solution containing hydrofluoric acid alone and a mixed acid aqueous solution obtained by mixing hydrofluoric acid and nitric acid are more preferable. The stock solution concentration of the acidic aqueous solution is appropriately set according to the strength of the acid used, and is, for example, preferably 0.7% to 100%, more preferably 0.7% to 40%. The temperature at the time of the acid treatment is preferably 25 to 90 ℃, more preferably 60 to 90 ℃, and the reaction time (immersion time) is preferably 15 to 80 minutes.
A preferable embodiment of the acid treatment step is a method in which the phosphor powder is added to an acidic solution and then stirred for a predetermined time. Thus, the reaction with the acid can be more reliably performed on the surface of the α -sialon phosphor particles. By stirring at a high speed, the acid treatment of the particle surface can be easily and sufficiently performed. The "high speed" here also depends on the stirring apparatus used, but when a laboratory-grade magnetic stirrer is used, the stirring speed is, for example, 400rpm or more, and in reality, 400rpm to 500rpm. If the stirring speed is about 200rpm for the purpose of ordinary stirring in which a new acid is continuously supplied to the particle surface, it is considered that the stirring speed is sufficient, and when the stirring is performed at a high speed of 400rpm or more, elements and compounds that do not contribute to fluorescence are sufficiently removed by physical action in addition to chemical action, and/or the chemical stability of the particle surface is improved.
As described above, the conditions that P1 is 70% or more and (P1-P2)/P1 × 100 is 2.8% or less, which are defined for the internal quantum efficiency after the heat treatment, can be controlled by optimally adjusting the stock solution concentration of the acidic aqueous solution used for the acid treatment, the temperature at the time of the acid treatment, the reaction time, the stirring speed, and the like. For example, with reference to the examples described later, the phosphor powder can be made to have desired values of P1 and (P1-P2)/P1X 100 by performing the acid treatment under conditions similar to the combination of the stock solution concentration of the acidic aqueous solution, the temperature at the time of the acid treatment, the reaction time, and the stirring speed.
(Complex)
The composite according to the embodiment includes the phosphor particles and a sealing material for sealing the phosphor particles. In the composite according to the present embodiment, a plurality of the phosphor particles are dispersed in the sealing material. As the sealing material, known materials such as resin, glass, and ceramics can be used. Examples of the resin used for the sealing material include transparent resins such as silicone resin, epoxy resin, and urethane resin.
Examples of the method for producing the composite include the following methods: the phosphor particles of the present embodiment are prepared by adding a powder composed of α -sialon phosphor particles to a liquid resin or a powdery glass or ceramic, uniformly mixing the mixture, and then curing or sintering the mixture by heat treatment.
(light-emitting device)
Fig. 1 is a schematic cross-sectional view showing a structure of a light-emitting device according to an embodiment. As shown in fig. 1, the light-emitting device 100 includes a light-emitting element 120, a heat sink 130, a case 140, a first lead frame 150, a second lead frame 160, a bonding wire 170, a bonding wire 172, and a composite 40.
The light emitting element 120 is mounted on a predetermined region of the upper surface of the heat sink 130. By mounting the light emitting element 120 on the heat sink 130, the heat dissipation of the light emitting element 120 can be improved. In addition, a substrate for package may be used instead of the heat sink 130.
The light emitting element 120 is a semiconductor element that emits excitation light. As the light emitting element 120, for example, an LED chip that generates light having a wavelength of 300nm to 500nm equivalent to that from near ultraviolet to cyan light can be used. One electrode (not shown) disposed on the upper surface side of the light-emitting element 120 is connected to the surface of the first lead frame 150 via a bonding wire 170 such as a gold wire. The other electrode (not shown) formed on the upper surface of the light-emitting element 120 is connected to the surface of the second lead frame 160 via a bonding wire 172 such as a gold wire.
The housing 140 is formed with a substantially funnel-shaped recess portion whose aperture gradually increases from the bottom surface upward. The light emitting element 120 is disposed on the bottom surface of the recess. The wall surface surrounding the recess of the light emitting element 120 functions as a reflection plate.
The composite 40 is filled in the recess formed in the wall surface by the case 140. The composite 40 is a wavelength conversion member that converts excitation light emitted from the light emitting element 120 into light of a longer wavelength. As the composite 40, the composite of the present embodiment is used, and the α -type sialon phosphor particles 1 of the present embodiment are dispersed in a sealing material 30 such as a resin. The light-emitting device 100 emits a mixed color of light from the light-emitting element 120 and light generated from the α -sialon phosphor particles 1 excited by absorbing the light from the light-emitting element 120. Light-emitting device 100 preferably emits white light by mixing light from light-emitting element 120 and light generated from α -sialon phosphor particle 1.
In the light-emitting device 100 of the present embodiment, as described above, when the internal quantum efficiency of the phosphor powder composed of the α -type sialon phosphor particles 1 after being held at 600 ℃ for 1 hour in the atmospheric atmosphere is P1 and the internal quantum efficiency after being held at 700 ℃ for 1 hour in the atmospheric atmosphere is P2, P1 is 70% or more and (P1-P2)/P1 × 100 is 2.8% or less, the fluorescent characteristics of the α -type sialon phosphor particles 1 and the composite 40 are improved, and the light emission intensity of the light-emitting device 100 can be improved.
Fig. 1 illustrates a surface-mount type light emitting device, and the light emitting device is not limited to the surface-mount type. The light emitting device may be of a cannon-shell type, a COB (chip on board) type, a CSP (chip scale package) type.
While the embodiments of the present invention have been described above, these are examples of the present invention, and various configurations other than the above-described configurations may be adopted.
Examples
The present invention will be further described below with reference to examples and comparative examples, but the present invention is not limited thereto.
(example 1)
The raw material powders were mixed in a glove box with 62.4 parts by mass of silicon nitride powder (E10 grade, manufactured by yukexing corporation), 22.5 parts by mass of aluminum nitride powder (E grade, manufactured by TOKUYAMA corporation), 2.2 parts by mass of europium oxide powder (RU grade, manufactured by shin-Etsu chemical corporation), and 12.9 parts by mass of calcium nitride powder (manufactured by high purity chemical research corporation), and the mixture was sieved with a 250 μm nylon sieve to obtain a raw material mixed powder. 120g of this raw material mixed powder was charged into a cylindrical boron nitride container (N-1 grade, manufactured by electrochemical Co., ltd.) with a lid having an internal volume of 0.4 liter.
The raw material mixed powder was subjected to a heating treatment for 16 hours at 1800 ℃ in a nitrogen atmosphere of atmospheric pressure in an electric furnace of a carbon heater together with a vessel. Since calcium nitride contained in the raw material mixed powder is easily hydrolyzed in the air, the boron nitride container filled with the raw material mixed powder is taken out from the glove box, and then quickly set in an electric furnace, and vacuum evacuation is immediately performed to prevent the reaction of calcium nitride.
The resultant was gently crushed with a mortar, and the whole was passed through a sieve having a mesh size of 150 μm to obtain a phosphor powder. The phosphor powder was examined for the crystal phase by powder X-ray Diffraction (hereinafter, referred to as XRD measurement) using CuK α rays, and as a result, the crystal phase existing was Ca — α sialon (Ca-containing α sialon) containing Eu element.
Then, 3.2ml of 50% hydrofluoric acid and 0.8ml of 70% nitric acid were mixed to prepare a mixed stock solution. 396ml of distilled water was added to the mixed stock solution, and the concentration of the mixed stock solution was diluted to 1.0% to prepare 400ml of a mixed acid aqueous solution. 30g of the phosphor powder composed of the α -sialon phosphor particles described above was added to this mixed acid aqueous solution, and in a 500ml beaker, the mixed acid aqueous solution was immersed for 30 minutes while being stirred at a rotation speed of 450rpm by a magnetic stirrer while being kept at a temperature of 80 ℃. The acid-treated powder was thoroughly washed with distilled water and filtered, and then dried, followed by passing through a sieve having a mesh size of 45 μm to obtain phosphor powder composed of α -sialon phosphor particles of example 1.
(example 2)
Phosphor powder composed of α -type sialon phosphor particles of example 2 was prepared in the same manner as in example 1 except that 396ml of distilled water was added to a mixed stock solution obtained by mixing 1.2ml of 50% hydrofluoric acid and 2.8ml of 70% nitric acid instead of the mixed acid aqueous solution used in example 1 to prepare a mixed acid aqueous solution having a stock solution concentration of 1.0%.
(example 3)
Phosphor powder composed of α -type sialon phosphor particles of example 3 was produced in the same manner as in example 1 except that 380ml of distilled water was added to a mixed stock solution obtained by mixing 10ml of 50% hydrofluoric acid and 10ml of 70% nitric acid instead of the mixed acid aqueous solution used in example 1 to prepare a mixed acid aqueous solution having a stock solution concentration of 5.0%, and the phosphor powder was immersed in the mixed acid aqueous solution at 30 ℃ for 30 minutes.
(example 4)
Phosphor powder composed of α -type sialon phosphor particles of example 4 was prepared in the same manner as in example 1 except that 300ml of distilled water was added to a mixed stock solution obtained by mixing 50ml of 50% hydrofluoric acid and 50ml of 70% nitric acid instead of the mixed acid aqueous solution used in example 1 to prepare a 25% stock solution mixed acid aqueous solution, and the phosphor powder was immersed in the mixed acid aqueous solution at 80 ℃ for 60 minutes.
Comparative example 1
Phosphor powder comprising α -sialon phosphor particles of comparative example 1 was prepared in the same manner as in example 1 except that 398ml of distilled water was added to a mixed stock solution obtained by mixing 1.0ml of 50% hydrofluoric acid and 1.0ml of 70% nitric acid to prepare a 0.5% stock solution, and that the temperature of the mixed acid aqueous solution was maintained at 80 ℃ in a 500ml beaker, and that acid treatment was performed for 30 minutes while stirring the mixed acid aqueous solution at a rotation speed of 300rpm with a magnetic stirrer, instead of the mixed acid aqueous solution used in example 1.
The stock solution concentration and the stirring rotation speed of the mixed acid aqueous solution used in comparative example 1 were set to the levels conventionally practiced.
(particle size measurement)
The particle size was measured by using a Microtrac MT3300EX II (Microtrac · Bel co.) and a particle size determined by the following method in accordance with JIS R1629:1997 by laser diffraction scattering. 0.5g of phosphor powder was put into 100cc of ion-exchanged water, and dispersed for 3 minutes by Ultrasonic Homogenizer U.S. Pat. No. 150E (manufactured by Nippon Seisakusho Co., ltd., chip size. Phi. 20, amplified 100%, oscillation frequency 19.5KHz, amplitude about 31 μm), after which particle size measurement was carried out by MT3300EX II. The median diameter (D) was determined from the particle size distribution obtained 50 )。
(luminescent Property)
The internal quantum efficiency and the external quantum efficiency at room temperature of each of the obtained phosphor powders were measured by a spectrophotometer (MCPD-7000, manufactured by Otsuka electronics Co., ltd.), and the calculation was performed in the following order.
Phosphor powder was filled in such a manner that the surface of the concave cuvette became smooth, and an integrating sphere was mounted. Monochromatic light split from a light emitting source (Xe lamp) into 455nm wavelength is introduced into the integrating sphere using an optical fiber. The sample of the phosphor powder is irradiated with the monochromatic light as an excitation source, and the fluorescence spectrum of the sample is measured.
A standard reflecting plate (Spectralon manufactured by Labsphere) having a reflectance of 99% was attached to the sample portion, and the spectrum of excitation light having a wavelength of 455nm was measured. At this time, the number of excitation light photons (Qex) was calculated from the spectrum in the wavelength range of 450nm to 465 nm.
Phosphor powder composed of α -sialon phosphor particles was attached to the sample portion, and the number of photons of excitation reflected light (Qref) and the number of photons of fluorescence (Qem) were calculated. The number of photons of the excitation reflected light was calculated in the same wavelength range as the number of photons of the excitation light, and the number of photons of the fluorescence was calculated in the range of 465nm to 800 nm.
Internal quantum efficiency = (Qem/(Qex-Qref)) × 100
External quantum efficiency = (Qem/Qex) × 100
When the standard sample NSG1301 sold by Sialon corporation was measured by the measurement method described above, the external quantum efficiency was 55.6% and the internal quantum efficiency was 74.8%. The apparatus was calibrated using this sample as a standard.
The internal quantum efficiencies after the heat treatment under the following 3 conditions were independently measured.
(1) After the phosphor powder was held at 600 ℃ for 1 hour, the internal quantum efficiency P1 was measured
(2) After the phosphor powder was held at 700 ℃ for 1 hour, the internal quantum efficiency P2 was measured
(3) After the phosphor powder was held at 800 ℃ for 1 hour, the internal quantum efficiency P3 was measured
The conditions for each heat treatment are as follows.
High temperature ambient furnace (atmosphere)
Sample holding method: closed type (holding sample in aluminum container with lid having inner volume of 30 cc)
(P1-P2)/P1X 100 (%) was calculated using the obtained P1 and P2. The results obtained for the internal and external quantum efficiencies are shown in table 1.
The peak wavelengths of the emission spectra of the phosphor powders obtained by the above measurement (excitation light wavelength: 455 nm) were all 600nm (larger wavelength) in examples 1 to 4.
(concentration C of Ammonia ion in phosphor powder) A Measurement of (2)
For the examples2, the concentration C of ammonia ions was measured according to the following procedure A 。
0.5g of phosphor powder was put into 25ml of distilled water in a PTFE container with a lid. The vessel containing the phosphor powder and distilled water was kept at 60 ℃ for 24 hours, and then the solid content was removed by filtration. The concentration of ammonia ions in the aqueous solution from which the solid matter was removed was measured by an ion chromatography apparatus (manufactured by Thermo Fisher Scientific Co., ltd.), and the total mass M of eluted ammonia ions was determined from the concentration and the amount of the aqueous solution A (unit: g). Then, with M A Divided by the mass of phosphor powder (0.5 g), multiplied by 10 6 Thus, the concentration C of the ammonium ion in the phosphor powder was determined A (unit: ppm).
(measurement of diffusion reflectance of phosphor powder)
The diffusion reflectance at a wavelength of 600nm of the phosphor powder of example 2 was measured in the following manner.
The diffuse reflectance was measured by mounting an integrating sphere device (ISV-722) in an ultraviolet-visible spectrophotometer (V-650) manufactured by Nippon spectral Co., ltd. A standard reflector (Spectralon) was used for baseline correction, a solid sample holder filled with phosphor powder was attached, and the diffuse reflectance with respect to light having a wavelength of 600nm was measured.
Various information on examples and comparative examples is summarized in table 1.
Although not shown in Table 1, the phosphor powder of example 2 had an ammonia ion concentration C A It was 29ppm. The phosphor powder of example 2 had a diffuse reflectance at a wavelength of 600nm of 94.8%.
[ Table 1]
Figure BDA0003281886710000131
As shown in Table 1, it was confirmed that the phosphor powders of examples 1 to 4 satisfying the conditions that P1 was 70% or more and (P1-P2)/P1X 100 was 2.8% or less improved both the internal quantum efficiency and the external quantum efficiency as compared with comparative example 1 not satisfying the conditions.
( The following comparative example was added: example 2 with the acid treatment conditions changed )
Phosphor powder composed of α -sialon phosphor particles was obtained in the same manner as in example 2, except that the stirring speed by a magnetic stirrer in the acid treatment was changed from 450rpm to 200rpm which is a normal level.
The median diameter D of the phosphor powder obtained in this additional comparative example 50 14.5 μm, a diffuse reflectance at a wavelength of 600nm of 93.5%, and a concentration C of ammonia ions in the phosphor powder A Was 113ppm.
The phosphor powder obtained in the additional comparative example had an internal quantum efficiency of 75.4% and an external quantum efficiency of 66.6%, which was inferior to that of example 2 (and other examples).
As can be understood from the results of the above additional comparative examples and the like:
the final phosphor powder was different between the case of "high-speed stirring" at a stirring speed of 450rpm in the acid treatment (example 2) and the case of "low-speed stirring" at 200rpm,
the phosphor powder obtained by low-speed stirring has poor light emission characteristics.
The present application claims priority based on japanese application No. 2019-069109, filed on 3/29/2019, the entire disclosure of which is incorporated herein by reference.
Description of the symbols
1. Alpha-sialon phosphor particle
30. Sealing material
40. Composite body
100. Light emitting device
120. Light-emitting element
130. Heat radiator
140. Shell body
150. First lead frame
160. Second lead frame
170. Bonding wire
172. Bonding wire

Claims (5)

1. A phosphor powder comprising Eu-containing alpha-sialon phosphor particles,
the Eu-containing alpha-sialon phosphor particle is represented by the general formula: (M1) x ，M2 y ，Eu z )(Si 12－(m+n) Al m+n )(O n N 16－n ) The Eu-containing alpha-sialon phosphor is characterized in that in the general formula, M1 is a 1-valent Li element, M2 is a 2-valent Ca element, x =0, y is more than 0 and less than 2.0, z is more than 0 and less than or equal to 0.5, x + y is more than 0 and less than or equal to 0.3 and less than or equal to 2.0, M is more than 0 and less than or equal to 4.0, n is more than 0 and less than or equal to 3.0,
when the internal quantum efficiency after being maintained at 600 ℃ for 1 hour under the atmosphere is P1, and the internal quantum efficiency after being maintained at 700 ℃ for 1 hour under the atmosphere is P2, P1 is more than 70%, and (P1-P2)/P1X 100 is less than 2.8%.
2. The phosphor powder according to claim 1, wherein the internal quantum efficiency P2 is 68% or more.
3. The phosphor powder according to claim 1 or 2, wherein the internal quantum efficiency P3 after being held at 800 ℃ for 1 hour is 68% or more.
4. A composite body is provided with: the phosphor powder according to any one of claims 1 to 3, and a sealing material for sealing the phosphor powder.
5. A light-emitting device is provided with: a light-emitting element that emits excitation light, and the complex according to claim 4 that converts the wavelength of the excitation light.
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